Method of producing naphthalenedicarboxylic acids and diaryldicarboxylic acids

Abstract

A method of producing naphthalenedicarboxylic acids by the oxidation of dialkyl-substituted naphthalene with a gas containing molecular oxygen under liquid phase conditions in an organic solvent and in the presence of a catalyst comprising copper and bromine, or a catalyst comprising copper, bromine and at least one kind of element/compound selected from the group of consisting of amine compounds and heavy metallic elements which are vanadium, manganese, iron, cobalt, nickel, palladium and cerium. And a method of producing diaryldicarboxylic acids by the oxidation of dialkyl-substituted diaryl compounds with a gas containing molecular oxygen in an organic solvent and in the presence of the same catalyst. These methods permit high yields of naphthalenedicarboxylic acids of high purity and of diaryldicarboxylic acids of high purity with the use of small amounts of catalyst.

What is claimed is: 
     
       1. A method of producing naphthalenedicarboxylic acids of the formula ##STR5## comprising: oxidizing dialkyl-substituted naphthalene of the formula ##STR6##  (wherein R and R' respectively represent an alkyl group selected from the group consisting of methyl, ethyl and isopropyl groups, and wherein R and R' are the same or different from each other, with a gas containing molecular oxygen under liquid phase conditions in the presence of a catalyst comprising copper and bromine in an organic solvent,   wherein the ratio of copper to bromine in the catalyst in numbers of atoms is 1:a, a being in the range of 0.1≦a≦100.   
     
     
       2. The method of producing naphthalenedicarboxylic acids as defined in claim 1, wherein the organic solvent comprises acetic acid. 
     
     
       3. The method of producing naphthalenedicarboxylic acids as defined in claim 1, wherein the catalyst further comprises manganese, and wherein the ratio of the copper to the bromine and the manganese in numbers of atoms is 1a:b, a being in the range of 0.1≦a≦100, b being in the range of 0.1≦b≦100. 
     
     
       4. The method of producing naphthalenedicarboxylic acids as defined in any one of claims 1, 2 and 3, wherein the dialkyl-substituted naphthalene is 2,6-diisopropylnaphthalene. 
     
     
       5. The method of producing naphthalenedicarboxylic acids as defined in claim 3, wherein the catalyst further comprises at least one kind of heavy metallic element selected from the group consisting of vanadium, iron, cobalt, nickel, palladium and cerium, and wherein the ratio of the copper to the bromine, the manganese and the heavy metal in numbers of atoms is 1:a:b:c, a being in the range of 0.1≦a≦100, b being in the range of 0.1≦b≦100, c being in the range of 0.1≦c≦100. 
     
     
       6. The method of producing naphthalenedicarboxylic acids as defined in claim 1, wherein the catalyst further comprises at least one kind of heavy metallic element selected from the group consisting of vanadium, iron, cobalt, nickel, palladium and cerium, and wherein the ratio of the copper to the bromine and the heavy metal in numbers of atoms, is 1:a:c, a being in the range of 0.1≦a≦100, c being in the range of 0.1≦c≦100. 
     
     
       7. The method of producing naphthalenedicarboxylic acids as defined in claim 1, wherein the catalyst further comprises an amine compound, and wherein the ratio of the number of atoms of the copper to the number of atoms of the bromine and the number of moles of the amine compound is 1:a:d, a being in the range of 0.1≦a 100, d being in the range of 0.1≦d≦100. 
     
     
       8. The method of producing naphthalenedicarboxylic acids as defined in claim 7, wherein the catalyst further comprises at least one kind of heavy metallic element selected from the group consisting of vanadium, manganese, iron, cobalt, nickel, palladium and cerium, and wherein the ratio of the number of atoms of the copper to the number of atoms of the bromine, the number of moles of the amine compound and the number of atoms of the heavy metal, is 1:a:d:e, a being in the range of 0.1≦a≦100, d being in the range of 0.123 d≦100, e being in the range of 0.1≦e≦100. 
     
     
       9. The method of producing naphthalenedicarboxylic acids as defined in any one of claims 7 and 8, wherein the amine compound is pyridine. 
     
     
       10. The method for producing naphthalenedicarboxylic acids as defined in claim 1, wherein the oxidation reaction is carried out at a reaction temperature between 150° C. and 220° C. 
     
     
       11. The method for producing naphthalenedicarboxylic acids as defined in claim 1, wherein the oxidation reaction pressure is at least 5 kg/cm 2 . 
     
     
       12. The method for producing naphthalenedicarboxylic acids as defined in claim 11, wherein the reaction pressure is in the range of 5 kg/cm 2  to 50 kg/cm 2 . 
     
     
       13. A method of producing diaryldicarboxylic acids of the formula ##STR7## wherein A' represents either direct bonding, O, SO 2  or CO, comprising: oxidizing a dialkyl-substituted diaryl compound of the formula ##STR8##  wherein A represents either direct bonding, O, S, SO 2 , CO, or CH 2 , and wherein R and R' respectively represent an alkyl group of 1 carbon to 6 carbons or an alicyclic hydrocarbon group, R and R' being the same or different from each other with a gas containing molecular oxygen under liquid phase conditions in the presence of a catalyst comprising copper and bromine in an organic solvent,     wherein the ratio of copper to bromine in the catalyst in numbers of atoms is 1:a, a being in the range of 0.1≦a≦100.   
     
     
       14. The method of producing diaryldicarboxylic acids as defined in claim 13, wherein the organic solvent comprises acetic acid. 
     
     
       15. The method of producing diaryldicarboxylic acids as defined in claim 13, wherein the catalyst further comprises manganese, and wherein the ratio of the copper to the bromine and the manganese in numbers of atoms is 1:a:b, a being in the range of 0.1≦a≦100, b being in the range of 0.1≦b≦100. 
     
     
       16. The method of producing diaryldicarboxylic acids as defined in any one of claims 13, 14 and 15, wherein the dialkyl-substituted diaryl compound is 4,4'-diisopropylbiphenyl. 
     
     
       17. The method of producing diaryldicarboxylic acids as defined in claim 15, wherein the catalyst further comprises at least one kind of heavy metallic element selected from the group consisting of vanadium, iron, cobalt, nickel, palladium and cerium, and wherein the ratio of the copper to the bromine, the manganese and the heavy metal in numbers of atoms is 1:a:b:c, a being in the range of 0.1≦a≦100, b being in the range of 0.1≦b≦100, c being in the range of 0.1≦c≦100. 
     
     
       18. The method of producing diaryldicarboxylic acids as defined in claim 13, wherein the catalyst further comprises at least one kind of heavy metallic element selected from the group consisting of vanadium, iron, cobalt, nickel, palladium and cerium, and wherein the ratio of the copper to the bromine and the heavy metal in numbers of atoms is 1:a:c, c being in the range of 0.1≦a≦100, c being in the range of 0.1≦c≦100. 
     
     
       19. The method of producing diaryldicarboxylic acids as defined in claim 13, wherein the catalyst further comprises an amine compound, and wherein the ratio of the number of atoms of the copper to the number of atoms of the bromine and the number of moles of the amine compound is 1:a:d, c being in the range of 0.1≦a≦100, d being the range of 0.1≦d≦100. 
     
     
       20. The method of producing diaryldicarboxylic acids as defined in claim 19, wherein the catalyst further comprises at least one kind of heavy metallic element selected from the group consisting of vanadium, manganese, iron, cobalt, nickel, palladium and cerium, and wherein the ratio of the number of atoms of the copper to the number of atoms of the bromine, the number of moles of the amine compound and the number of atoms of the heavy metal is 1≦a:d:e, a being in the range of 0.1≦a≦100, d being in the range of 0.1≦d≦100, e being in the range of 0.1≦e≦100. 
     
     
       21. The method of producing diaryldicarboxylic acids as defined any one of claims 19 and 20, wherein the amine compound is pyridine. 
     
     
       22. The method for producing diaryldicarboxylic acids as defined in claim 13, wherein the oxidation reaction is carried out at a temperature between 150° C. and 220° C. 
     
     
       23. The method for producing diaryldicarboxylic acids as defined in claim 13, wherein the oxidation reaction pressure is at least 5 kg/cm 2 . 
     
     
       24. The method for producing diaryldicarboxylic acids as defined in claim 23, wherein the oxidation reaction pressure is in the range of 5 kg/cm 2  to 50 kg/cm 2 .